WO1993014131A1 - Process for producing copolymer latex and use thereof - Google Patents

Abstract

A process for producing copolymer latex by the emulsion polymerization of an aliphatic conjugated diene monomer and another monomer copolymerizable therewith in the presence of a cyclic unsaturated hydrocarbon having one unsaturated bond in the ring, characterized in that the addition of a monomer mixture containing the diene monomer is followed by the addition of another monomer mixture free from the diene monomer, or that part of a chain transfer agent is added after the addition of the monomers. The obtained latex is useful as an adhesive composition, paper coating composition, carpet backing adhesive composition, rock fiber base adhesive composition, gravure paper coating composition, color developing agent composition for pressure-sensitive paper, and the like.

Description

 Specification

 Method for producing copolymer latex and use thereof

 Industrial applications

 The present invention relates to a novel method for producing a copolymer latex and its use using a copolymer latex obtained by the production method.

 Conventional technology

 It is well known that so-called butadiene-based copolymer latex containing butadiene as a main component is widely used as a binder in the paper coating field, car backsizing, or for rock fiber substrates. It is about to be. .

 The performance required of the binder in each application is diverse, and the composition and structure of the butadiene-based copolymer latex are generally changed accordingly.

 These copolymer latexes are generally produced by emulsion polymerization.At this time, although there are some differences depending on the composition of the monomer mixture constituting the copolymer latex and the types and amounts of various additives, However, there was a problem that a fine coagulated product was generated in the copolymer latex.

 Such fine coagulates adhere to the reactor and have various adverse effects on the reaction process, and also cause various adverse effects in each end use.

 That is, in the field of paper coating, if such coagulated matter is large, problems such as streak trouble at the time of blade coating, applicator contamination, separation at the time of calendering, blanket piling at the time of printing, and the like occur.

Furthermore, these copolymer latexes are used for adhesives for carpet backing such as tufted carpet needle punch carpets, car cushion materials, civil engineering mats, industrial filters, etc. Rock fiber used for It is also used as an adhesive for textile substrates, but even in this case, the fine coagulated material in the copolymer latex adversely affects the adhesive strength and water resistance.

 As described above, the fine coagulated product in the copolymer latex is usually removed by a filtration step or the like because it causes contamination of the reactor and causes various adverse effects in each end use.

 However, the filtration process is also complicated, and the amount of the fine coagulated material to be removed is limited. Therefore, it is difficult to completely remove the fine coagulated material, and the productivity has been reduced.

 In the field of paper coating, it has been promoted to increase the coating speed when producing coated paper from a reasonable point of view, and paper coating compositions with better high-speed coating suitability than before have been promoted. Things are required.

 Furthermore, not only the coating speed but also the printing speed on coated paper have been increased, and high-speed printing suitability superior to the past has been achieved.

 In other words, paper coating compositions are required to have excellent fluidity and mechanical stability during high-speed coating, and coated papers are required to have excellent adhesive strength, blister resistance, and print gloss. .

 Among them, particularly the adhesive strength has been improved by increasing the proportion of aliphatic conjugated gen (butadiene), which is one component in the copolymer latex. This is to improve the adhesive strength by increasing the tackiness of the copolymer latex, but this method causes the following operational problems when producing coated paper. .

In general, most paper used for printing paper is coated on both sides. In such double-sided coating, first, the first coater is used for single-sided coating, and after the dry explosion, the second coating is used to coat the backside, and the coating layer on the front side supports the paper. Sticking on rolls, accumulating, and dirtying rolls, so-called backing A phenomenon called roll contamination occurs. When such roll dirt occurs, not only does the coated paper properties such as smoothness and gloss decrease, but also the coating must be interrupted to wash the roll dirt. Will be reduced.

 Such backing roll stains are considered to be one of the g factors of the tackiness of the copolymer latex used as a binder. Thus, in order to improve the adhesive strength of the coated paper, simply use the copolymer. Increasing the proportion of aliphatic conjugated diene in the latex will result in increased backing roll fouling.

 For this reason, improvement of the above copolymer latex to solve this problem has been conventionally studied, but none of these conventional copolymer latexes has been sufficiently satisfactory.

 Therefore, there is a strong demand for a copolymer latex capable of providing a coated paper having an excellent balance of adhesive strength and anti-backing roll stain resistance that can respond to recent high-speed printing.

 Furthermore, these copolymer latexes often have a problem of odor caused by alkyl mercaptan used as a chain transfer agent. Since this odor particularly reduces the commercial value of the final product, there is a need for a copolymer latex that generates less odor.

 In addition, gravure printing is a so-called intaglio printing in which the ink filled in the recesses of the plate is printed on paper. Compared with offset printing (lithographic printing), gravure printing has a greater amount of ink deposition and excellent gradation reproducibility. You can obtain printed materials with a rich sense of volume and richness. For this reason, it has been spreading rapidly, along with the recent colorization and visualization of magazines.

To fully demonstrate the features of gravure printing, Coated paper for gravure printing which is excellent in quality is generally used. Coated paper for gravure printing is designed to minimize ink transfer leakage from the individual cells of the gravure plate during printing by improving smoothness, cushioning properties, oil absorption, etc., as much as possible. Although it has much better suitability for gravure printing than ordinary coated paper, it has been required to have even better suitability for Dalavia printing due to the recent increase in printing speed.

 On the other hand, in the production process of coated paper for gravure printing, attempts have been made to apply the coating at a faster speed than before in order to improve productivity. However, as the coating speed increases, operational problems such as streaking and bleeding due to the fluidity and water retention of the coating material are more likely to occur, and the suitability of the final product coated paper for gravure printing is also increased. Therefore, it is strongly desired to solve these problems.

 In general, pressure-sensitive copying paper is coated on the back with fine capsules containing a colorless or pale-colored leuco dye, which is electrophilic, dissolved in an organic solvent (force oil), and an electron-accepting developer. It is composed of a base paper with a color developing layer on the surface, and these two types of coated surfaces are overlapped so that they face each other, and the pressure is applied by applying pressure with a ball-bench or a typewriter. The capsule is destroyed, and the capsule oil containing the leuco dye is transferred to the color developing layer to perform a color-forming reaction so that a print record can be obtained.

Such pressure-sensitive copying paper has become widespread because it is more aesthetically pleasing than conventional copying methods using carbon paper and does not stain clothes or hands. Due to its characteristics, pressure-sensitive copying paper is most widely used as slip paper, but in this case several copies may be required at one time. In such a case, the so-called middle paper coated with a developing layer on the front and a capsule on the back, between the upper paper and the lower paper It is common to insert one or several sheets into a single sheet. However, the more the middle paper is inserted, the lower the printing pressure and pen pressure transmitted to the lower paper, and there is a problem that the color developability is reduced.

 In addition, such pressure-sensitive paper is often used outdoors. However, especially in a cold region in winter, there is a problem that the so-called low-temperature initial coloring property immediately after copying is poor. On the other hand, offset printing is often performed on the color developing layer of the middle or lower paper, and if the adhesive strength of the color developing layer is low, there is a problem that paper dusting occurs during printing. In order to solve these problems, pigments having a specific latex or a specific particle size are disclosed in JP-A-60-24992 and JP-A-6-83093. Attempts have been made to use. However, even with these methods, the low-temperature initial color development was sufficiently improved.

 Disclosure of the invention

 The present inventors have conducted intensive studies on the above problems, and as a result, obtained by emulsion polymerization of a monomer mixture in the presence of a specific compound, and in the emulsion polymerization, an aliphatic conjugated monomer. After the addition of the monomer mixture containing the monomer, a monomer mixture containing no such component is added, and in the emulsion polymerization, a part of the chain transfer agent is added after the addition of the monomer is completed. As a result, the inventors have found that the above problems can be solved, and have reached the present invention.

 DETAILED DESCRIPTION OF THE INVENTION Hereinafter, the present invention will be described in detail.

Examples of the aliphatic conjugated diene monomer in the present invention include 1,3-butadiene, 2-methyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene, and 2-chloro-1,3. —Butadiene, substituted linear conjugated pentagens, substituted and side chain conjugated hexadenes, etc., one or more Can be used. In particular, 1,3-butadiene is preferred.

 Examples of the ethylenically unsaturated carboxylic acid monomer include mono- or dicarboxylic acids (anhydrous) such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, and itaconic acid.

 Other monomers copolymerizable with the aliphatic conjugated diene monomer and the ethylenically unsaturated ruponic acid monomer include alkenyl aromatic monomers, unsaturated carboxylic acid alkyl ester monomers, Examples include an unsaturated monomer containing a hydroxyalkyl group, a vinyl cyanide monomer, and an unsaturated carboxylic acid amide monomer.

 Examples of the alkenyl aromatic monomer include styrene, -methylstyrene, methyl-methylstyrene, vinyltoluene, divinylbenzene, and the like, and one or more kinds can be used. Styrene is particularly preferred.

 Examples of the unsaturated carboxylic acid alkyl ester monomer include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, glycidyl methacrylate, dimethyl fumarate, dimethyl fumarate, dimethyl maleate, and getyl maleate. Dimethylaconate, monomethyl fumarate, monoethyl fumarate, 2-ethylhexyl acrylate and the like, and one or more kinds can be used. Particularly, methyl methacrylate is preferred.

Examples of the unsaturated monomer containing a hydroxyalkyl group include / 5-hydroxysethyl acrylate, ^ -hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate, and hydroxybutyl acrylate. Butyl methacrylate, 3-chloro-2-hydroxypropyl methacrylate, G (ethylene dalicol) male Ethyl, di (ethylene glycol) itaconate, 2-hydroxyhexyl maleate, bis (2-hydroxyxethyl) maleate, 2-hydroxyethyl methyl fumarate, etc. it can. Particularly preferred is hydroxydemethylacrylate.

 Examples of the vinyl cyanide monomer include acrylonitrile, methacrylonitrile, monochloroacrylonitrile, α-ethylacrylonitrile, and the like, and one or more kinds can be used. Acrylonitrile is particularly preferred.

 Examples of the unsaturated carboxylic acid amide monomer include acrylamide, methacrylamide, Ν-methylol acrylamide, Ν-methylol methacrylamide, Ν, Ν-dimethylacrylamide and the like. Two or more types can be used. Acrylamide is particularly preferred.

 Although there is no particular limitation on the monomer composition, particularly in the inventions of claims 1, 12 and 13, the aliphatic conjugated diene monomer 10 to 80% by weight, ethylene The unsaturated carboxylic acid monomer is preferably 0.5 to 10% by weight and another monomer copolymerizable therewith, preferably 10 to 89.5% by weight. When the amount of the aliphatic conjugated diene monomer is less than 10% by weight, the adhesive strength tends to be low, and when the amount exceeds 80% by weight, the water resistance tends to be poor.

 If the amount of the ethylenically unsaturated carboxylic acid monomer is less than 0.5% by weight, the mechanical stability is poor, and if it exceeds 10% by weight, the viscosity of the latex tends to increase, which is not preferable.

 If the amount of the other copolymerizable monomer is less than 10% by weight, water resistance is obtained, and if it exceeds 89.5% by weight, the adhesive strength tends to be poor, which is not preferable.

In particular, the monomer composition of the copolymer latex used as the binder for gravure printing of the invention according to Item 8 is preferably an aliphatic conjugated monomer 30 to 80% by weight, 0.5 to 10% by weight of an ethylenically unsaturated carboxylic acid monomer, and 10 to 69.5% by weight of another monomer copolymerizable therewith.

 When the amount of the aliphatic conjugated diene monomer is less than 30% by weight, the obtained coated paper is inferior in Dalavia printability, and when the amount exceeds 80% by weight, whirl stains occur during the super calendar treatment of the coated paper. Is not preferred. If the amount of the ethylenically unsaturated carboxylic acid monomer is less than 0.5% by weight, the mechanical stability of the copolymer latex is poor, and if it exceeds 10% by weight, the viscosity of the copolymer latex becomes high. Not preferred. If the amount of the other copolymerizable monomer is less than 10% by weight, the resulting coated paper will be stained with rolls during the super-force rendering treatment, and if it exceeds 69.5% by weight, the coated paper will not be coated. Gravure printing suitability is poor, which is not preferable.

 Further, the monomer composition of the copolymer latex used as the binder for the pressure-sensitive copying paper according to the invention of the tenth aspect is 20 to 60% by weight of an aliphatic conjugated diene monomer, It is 0 to 20% by weight of a vinyl monomer, 1 to 20% by weight of an ethylenically unsaturated carboxylic acid monomer, and 0 to 79% by weight of another monomer copolymerizable therewith.

 If the amount of the aliphatic conjugated diene monomer is less than 20% by weight, the adhesive strength will be poor. If the content of the vinyl cyanide-based monomer exceeds 20% by weight, the adhesive strength is inferior, which is not preferable. If the amount of the ethylenically unsaturated sulfonic acid monomer is less than 1% by weight, the mechanical stability is poor, and if it exceeds 20% by weight, the adhesive strength is inferior. If the amount of the other copolymerizable monomer exceeds 79% by weight, the adhesive strength is poor, which is not preferable. Further, the copolymer latex used as a binder for pressure-sensitive copying paper according to the invention of paragraph 8 has a gel content in the range of 50 to 100% from the viewpoint of color developability and printability. It is preferable that

In addition, in particular, the method of the invention of paragraph 12, that is, a part of the chain transfer agent By adopting the method of adding after the addition of the body, it is possible to obtain a copolymer latex having a better balance between blister resistance and adhesive strength.

 In this case, the ratio of the chain transfer agent added after the completion of the monomer addition to the total amount of the chain transfer agent used is not particularly limited, but is preferably 30% by weight or less.

 Further, the method according to the invention of Item 13, that is, after the addition of the monomer mixture containing the aliphatic conjugated diene monomer (i) component among the above monomers,

When a method of adding a monomer mixture containing no component (a) is employed, a copolymer latex having a particularly excellent balance between adhesive strength and backing roll stain resistance can be obtained.

 In this case, the amount of the monomer mixture containing no (ii) component added in the latter half is preferably in the range of 3 to 40% by weight based on the total amount of the monomers used (total). No.

Examples of the chain transfer agent used in the present invention include n-hexyl mercaptan, _π -octyl mercaptan, t-octyl mercaptan, n-dodecyl mercaptan, butododecyl mercaptan, and η-stearyl mercaptan. Xanthogen compounds such as alkylmercaptan, dimethylxanthogen disulfide, diisopropylpyrxantogen disulfide, monomethylstyrene dimer, terpinolene, tetramethylthiuram disulfide, tetraethylthiuram disulfide, tetramethylthiuram monosulfide Thiuram-based compounds, such as 2,6-di-tert-butyl-4-methylphenol, phenol-based compounds such as styrenated phenol, diaryl compounds, aryl compounds such as aryl alcohol, dichloromethane, dibromomethane, tetrachloride carbon , Halogenated hydrocarbon compounds such as carbon tetrabromide, etc., Vinyl ethers such as zircoxyacrylonitrile and benzyloxyacrylamide, triphenylurethane, pentaphenylethane, acrolein, methacrolein, thioglycolic acid, thiomalic acid, 21 Ethylhexylthioglycolate, etc., and one or more kinds can be used.

 The use amount of these chain transfer agents is not limited at all, and can be appropriately adjusted according to the performance required for the copolymer latex.However, the amount is preferably 0.1 to 100 parts by weight of the monomer mixture. It is 0.5 to 10 parts by weight.

 -Most of the cyclic unsaturated hydrocarbon having one unsaturated bond in the ring used in the present invention remains unreacted after the completion of polymerization, and it is necessary to recover the unreacted product. Therefore, those having a boiling point of 140 ° C. or less are preferred. Specific examples include cyclopentene, cyclohexene, cycloheptene, 4-methylcyclohexene, and 1-methylcyclohexene, and cyclopentene, cyclohexene and cycloheptene are particularly preferably used.

 The amount of the compound used in the present invention is 0.1 to 30 parts by weight based on 100 parts by weight of the monomer mixture. When the amount is less than 0.1 part by weight, the effect of the present invention is insufficient, and when the amount exceeds 30 parts by weight, the amount of the compound remaining as an unreacted substance also relatively increases, and the energy required for the recovery is large. It is not good because it becomes. Preferably it is 0.5 to 15 parts by weight, more preferably 1 to 15 parts by weight.

 The method for adding the various components in the present invention is not particularly limited, and any of a batch addition method, a split addition method, and a continuous addition method can be employed. Further, in the emulsion polymerization, a commonly used emulsifier, polymerization initiator, electrolyte, polymerization agent, chelating agent and the like can be used.

Further, in the present invention, any of single-stage polymerization, two-stage polymerization, multi-stage polymerization, etc. In particular, in the inventions of the first, eighth and tenth aspects, it is preferable to carry out emulsion polymerization by the following method.

 That is, as the first stage, 3 to 40% by weight, preferably 5 to 30% by weight of the monomer is polymerized with respect to all the monomorphs, and the polymerization conversion of the first stage is 50% or more, Preferably, when the concentration is 70% or more, the remaining monomers are added to substantially complete the polymerization.

 In particular, in the invention of Item 12, emulsion polymerization is preferably performed by the following method.

 That is, as the first stage, 3 to 40% by weight, preferably 5 to 30% by weight, of the monomer or a part of the monomer and the chain transfer agent is added to all the monomers. When the polymerization conversion of the first stage reaches 50% or more, the remaining monomer or the second stage monomer and a part of the chain transfer agent are added as the second stage. After completion of the second-stage monomer addition, a part of the chain transfer agent is further added to continue the polymerization, thereby substantially completing the polymerization.

 Further, in particular, in the invention of Item 13, it is preferable to carry out emulsion polymerization by the following method.

 That is, as the first stage, a monomer containing 3 to 40% by weight, based on the total monomers, of an aliphatic co-functional monomer (a) and an ethylenically unsaturated carboxylic acid monomer (a mouth) The mixture was added and polymerization was carried out. After that, a monomer mixture containing 20 to 94% by weight of the aliphatic conjugated diene monomer (a) was added as a second stage, and then a third stage was carried out. It does not contain 440% by weight of the component (a), and the polymerization is continued by adding the monomer mixture to substantially complete the polymerization.

Examples of the emulsifier used in the present invention include higher alcohol sulfates, alkylbenzene sulfonates, alkyl diphenyl ether sulfonates, aliphatic sulfonates, aliphatic carboxylates, and nonionic surfactants. Examples thereof include anionic surfactants such as sulfate esters and nonionic surfactants such as alkyl ester type, alkyl phenyl ether type, and alkyl ether type of polyethylene glycol.One or more of these are fflt , Rel.

 As the initiator, a water-soluble initiator such as potassium persulfate, ammonium persulfate or sodium persulfate, an oil-soluble initiator such as a redox initiator or benzoyl peroxide is used.

 By adopting the above-mentioned production method, it is possible to suppress the generation of fine coagulated products and obtain a copolymer latex having good polymerization stability. Since cyclic unsaturated hydrocarbons having one saturated polymerization are not preferable in terms of working environment hygiene in final use, in the present invention, after the copolymer latex is polymerized by the production method, it remains as an unreacted product. The compound is substantially removed (0.5 parts by weight or less, more preferably 0.1 part by weight or less based on 100 parts by weight of the copolymer latex (solid content)).

 The compound can be removed by a known method, for example, steam distillation, distillation under reduced pressure, or blowing of an inert gas.

 Further, the present invention provides various adhesive compositions containing the copolymer latex produced by the above method.

 For example, a composition for paper coating, an adhesive composition for a car backing, an adhesive composition for a rock fiber base, an adhesive composition for a tire cord, an adhesive composition for wood, an adhesive composition for leather It can be used as a product.

The paper coating composition according to the inventions of the first, second and third aspects is prepared as an aqueous dispersion together with the copolymer latex, a pigment and, if necessary, other binders. At this time, the copolymer latex of the present invention is used in an amount of 2 to 100 parts by weight, preferably 5 to 30 parts by weight, and other binder, based on 100 parts by weight of the pigment in terms of solid content. Up to 30 parts by weight can be used.

 Here, examples of the pigment include inorganic pigments such as kaolin clay, talc, barium sulfate, titanium oxide, calcium carbonate, aluminum hydroxide, zinc oxide, and satin white; and organic pigments such as polystyrene latex. Or used mixed.

 Other binders include modified starches such as starch, oxidized starch, and esterified starch; natural binders such as soy protein, casein; and synthetic latexes such as polyvinyl alcohol, polyvinyl acetate latex, and acrylic latex. Is done.

 To prepare the paper coating composition of the present invention, other auxiliary agents such as dispersants (sodium pyrophosphate, sodium polyacrylate, sodium hexamethaphosphate, etc.), defoamers (polyglycol, fatty acid ester) , Phosphate esters, silicone oils, etc.), leveling agents (funnel oil, dicyan diamide, urea, etc.), preservatives, waterproofing agents (formalin, hexamine, melamine resin, urea resin, glyoxal, etc.), release Molding agents (calcium stearate, paraffin emulsion, etc.), fluorescent dyes, and color water retention improvers (carboxymethylcellulose, sodium alginate, etc.) are added as necessary.

 The method of applying the paper coating composition of the present invention to coated paper is performed by a known technique, for example, an applicator such as an air knife coater, a blade coater, a roll coater, or a bar coater. After application, the surface is dried and finished by force rendering.

The adhesive composition for backing a carpet according to the present invention comprises the above-mentioned copolymer latex. And z and other additives.

 At that time, the filler can be used in an amount of 0 to 800 parts by weight based on 100 parts by weight of the copolymer latex in terms of solid content.

 Examples of the filler include calcium carbonate, aluminum hydroxide, hollow glass spheres, clay, tanolek, silica, and carbon black. These can be used alone or in combination.

 Other additives include commonly used pH adjusters, emulsifiers, stabilizers, vulcanizing agents, vulcanization accelerators, antioxidants, dispersants, defoamers, preservatives, thickeners, coloring agents , A crosslinking agent, a crosslinking aid and the like.

 In addition to the copolymer latex described above, the adhesive composition for a mouth fiber base material according to the present invention may further include a filler, an emulsifier, a stabilizer, an antioxidant, and a UV-deterioration inhibitor which are generally added. , Vulcanizing agents, vulcanization accelerators, dispersants, defoamers, preservatives, thickeners, coloring agents, crosslinking agents, crosslinking aids and the like can be added.

 Further, the gravure printing paper coating composition according to the invention of Item 8, is prepared as an aqueous dispersion together with the copolymer latex, a pigment, and if necessary, other binders, a thickener, and auxiliaries. You.

 At this time, 3 to 20 parts by weight, preferably 4 to 10 parts by weight, of the copolymer latex of the present invention is blended with 100 parts by weight of the pigment in terms of solid content.

 Here, the same pigments, other binders, thickeners, and auxiliaries as described above are used.

 Further, the color developer composition for pressure-sensitive copying paper according to the invention of Item 10, is characterized in that the copolymer latex is blended with a pigment, a color developer and, if necessary, other thickeners, assistants, etc. Prepared.

Pigments include heavy calcium carbonate, light calcium carbonate, kaolin, calcined kaolin, aluminum hydroxide, talc, silica powder, barium sulfate, Titanium oxide, satin white, plastic pigment, etc. used for general coated paper are used alone or in combination of two or more.

 Examples of the color developing agents include, for example, acidic clay, activated clay, clay materials such as attapulgite, zeolite, bentonite, kaolin, metal salts of aromatic carboxylic acids, and fuynol resins. Developers can be used.

 Other thickeners and binders include, for example, proteins (gelatin, albumin, casein, etc.), starches (cereal starch, oxidized starch, oxidized starch, etherified starch, esterified starch, etc.), cell α- Water-soluble natural polymer compounds such as derivatives (carboxymethylcellulose, hydroxypropylcellulose, methylcellulose, etc.), polyvinyl alcohol, acrylamide-modified polyvinyl alcohol, polyvinylpyrrolidone, polyacrylic acid, polyacrylamide, and maleic acid. A water-soluble synthetic polymer compound such as a polymer is used.

 Other auxiliaries include ρΗ adjusters, emulsifiers, stabilizers, release agents, antioxidants, dispersants, defoamers, preservatives, coloring agents, crosslinking agents, crosslinking assistants, etc., which are commonly added. Is mentioned.

 The copolymer latex in the present invention is usually used in an amount of 5 to 40 parts by weight based on 100 parts by weight of the pigment.

The developer is usually used in an amount of 5 to 40 parts by weight based on 100 parts by weight of the face. Further, it is preferable that a color developer such as a metal salt of an aromatic carboxylic acid or a fuanol resin is previously blended as an aqueous dispersion by a ball mill, a sand mill or the like. The thus-prepared developer composition for pressure-sensitive copying paper can be used with a commonly used coating machine such as a blade coater, a roll coater, a knife coater, an air knife coater, and a curtain coater. Paper, synthetic paper, synthetic film, etc. Coated on a suitable substrate.

 Example

 Hereinafter, the present invention will be more specifically described with reference to examples, but the present invention is not limited to these examples. In the examples, parts and% are based on weight. The measurement of various physical properties in the examples was based on the following methods.

 Reactor dirt

 After the polymerization, visually observe the deposits on the inner wall of the reactor and evaluate according to the following criteria: o: Very low

 △: less-

X: Many

 Fine coagulated material

 Number / π present in latex! Observe microscopic solids of ~ 50 / im under a microscope and evaluate according to the following criteria:

 〇: very little

 Few

 X: Many

Gel content

 A latex film is prepared by drying at room temperature. Thereafter, about 1.0 g of the latex film is accurately weighed, put in 40 Occ of toluene, left for 48 hours to dissolve, filtered through a 300 mesh wire mesh, dried, and dried with toluene insoluble matter on the wire mesh. Weigh (gel) and calculate gel content.

Example of polymerization of copolymer latex 1

In a 10 liter autoclave, 100 parts of water, 0.3 part of sodium dodecylbenzenesulfonate, 0.2 part of sodium bicarbonate, potassium persulfate 1. Charge 0 parts and the first-stage monomer mixture shown in Table 1 or Table 2, a chain transfer agent, and a cyclic unsaturated hydrocarbon having one unsaturated bond in the ring. Was polymerized. When the conversion of the first-stage emulsion polymerization reaches 70%, the second-stage polymerization is performed by continuously adding the monomer mixture, the chain transfer agent, and the unsaturated hydrocarbon in the second-stage for 7 hours. Was. Thereafter, in order to complete the polymerization, the reaction was continued for another 3 hours to complete the polymerization. All polymerization conversions were 98% or more. After adjusting the pH of the obtained copolymer latex to 8 using sodium hydroxide, unreacted monomers and unsaturated hydrocarbons remaining as unreacted substances are removed by steam distillation to obtain a copolymer. Latex 1-13 was obtained.

 In the table, the left side shows the amount of the first stage and the right side shows the amount of the second stage across "Z". Preparation of composition for paper coating

 Using a copolymer latex 1 to 13, a paper coating composition was prepared using pure water so as to have a solid content concentration of 60% based on the following formulation. The mechanical stability and fluidity of the obtained paper coating composition were measured. (Prescription)

 Kaolin clay 80 parts

 Calcium carbonate 20 parts

 Modified starch 6 parts

 '' 1 to 2 parts of copolymer latex (solid content)

After coating with a coating bar so that the coating amount of the above composition is 1 O gZm ^{2 on} one side on a commercial high-quality paper (64 gZm ² ), the coating is dried, and the roll temperature is 50 ° C Super calendering was performed under a pressure of 70 to 80 kg / cm to obtain a coated paper.

The obtained coated paper was measured for RI Wet Pick, RI Dry Pick, blister resistance, print gloss and odor. Mechanical stability

 The above coating composition is kneaded between a metal port and a rubber port using a putter tester, subjected to mechanical shearing, and the time (minutes) until a coagulated product is formed on a rubber roll is measured. .

 〇: 30 minutes or more

 △: 20 minutes or more and less than 30 minutes

 X: less than 20 minutes

 Liquidity

 The viscosity of the paper coating composition is measured using a Hercules high-shear viscometer at a rotational speed of 400 O rpm using Pop F. The lower the viscosity, the better the fluidity. R I Wet Pick

 The degree of picking when printing using dampening water with an RI printing machine was visually judged, and evaluated by a five-grade method from grade 1 (best) to grade 5 (worst). . The average of 6 measurements is shown.

 R I Dry Pick

 Except that no dampening solution is used, the book is prepared in the same manner as in the above R I Wet Pick and blister resistance

 Condition the humidity of duplex coated paper (about 6 and throw it into a heated oil bath to indicate the minimum temperature at which blisters occur.

Printing gloss

 Perform constant-speed printing using a commercially available red ink for offset printing using an RI printing machine to prepare samples. The gloss of the printed surface of the sample is measured according to the method of JISP-8141. The higher the value, the better the gloss.

Odor A coated paper was obtained in the same manner as the coating method described above, except that the coating amount of the paper coating composition was 2 OgZm ^{2 on} one side. From the obtained coated paper, prepare a test piece of l Ocnix 1 Ocm, put three test pieces in a glass bottle that can be hermetically sealed, leave it at 50 1 for 1 hour, remove 拴, and measure the degree of odor. Judged.

 X: Smell

 △: Somewhat smell

 〇: Almost no smell

-19- New paper Anti-weakness mesme t-methane A-A0, * 0

 Table

 Chita Hikuku

 Kukukuku

 Tono out

 No. Example

 Retakuro 0

 Latex

 Maki N Chimeri o. 2 3 4 5 6 7 Rishi

 Evening Rotage 3/24 2/28 5/25 4/30 2/33

 Lucoli 4/36 7/38 Kuni 5/42 3/47 9/50 5/42 2/34. 5 4/38 5/25

, Nire 2/18 1/9 5/2. 5 — / 5 2/23 2/8 -Ruakipukien Reli-/ 3 5/2. 5 1/9 2/13

 Toklund L 1/4 1/9 Rusatesse Temiliri 1 1/1 1 /-1 / —1 / 1 /

 2 / — 1 / one 1 / one

 Acid acid acid 2 / —1.5 /-

2 II-3

to 2 / ~ 4 n o 1 / one one / 1

 o ぺ 3 /-

To P 5 3 / I 3 / — 5/3

 To the mouth 2 / — 3 to the mouth

 Methyl stylenda

 0. 3 / — 0, 3 / —

 Do not print

 1-/ 0. 6 0, 1/0. 3 0. 1/0. 9 0. 1/0. 4 0. 1/0. 3 0. 1/0. 4 Pinolen 0.3./

 Dirty 〇 凝 凝 凝 有 〇 Yes 38 82 78

〇〇5

〇〇 ^

Table 1 2

 Example Example Comparative Example

Latex No. SQ in 1 11 19 L 110Q Buta 5/45 6/54 3/27 7/38 4/30 2/33 Styrene 4/37 3/26 6/51 6/37 5/42 2 / 34.5 Metinole Met Crate Rate 1/4 1/5 1/4 1/9 ~ / 5 2/23 End Cle — Trinole / O 1 IA 1 / Q

 I / O

Metafreeloni

De β--Hydroxishetinorea creat 1 / -1 1/1 / 1-1 / 1/1

 r 1 / monofumanoleic acid 2 / — 1 / mono1.5 /-itaconic acid? / — 1 • XI—

 0 /

Ma

 Kuri Nore

 Cyclopenten Li-

 Cyclohexane 4 /-Cyclohexane 2 /-Cyclic norenene 6 /-a — methyl styrene dimer

t-decinol-mel-captan 0.1 / 0.5-/ 0.5 0.1 / 0.6 0.1 / 0.7 0.1 / 1.0 0.1 / 0,5 Tapinolene

Reactor contamination 〇 XX △ mm Fine solids 〇 XX ΔX Gel included 78 85 48 83 59 69

Table 3 Example Comparative Example Latex No. 1 2 3 4 5 6 7 8 9 lu 11 1 ο 13 One coating composition One mechanical stability 〇 〇 〇 〇 〇 〇 〇 〇 XX XX △ Δ Fluidity (CPS) 45 51 53 48 44 48 50 48 47 61 65 58 57 Coated paper properties

 RI Dry Pick 3.2 2.9 2.5 2.0 1.8 1.5 1.3 1.3 1.2 3.3 2.2 2.2 2.1 Flip resistance, Lister resistance (° C) 245 255 240 225 215 205 210 210 210 200 215 195 210 205

RI Wet Pick 1.8 1.5 1.2 1.8 2.2 2.0 3.1 3.1 3.4 2.3 3.5 2.2 2.8 Odor 〇 〇 〇 〇 〇 〇 〇 〇 XXX 印刷 Print gloss (%) 80 83 80 84 82 84 82 81 82 77 75 78 79

Polymerization example 2 of copolymer latex

 In a 10-liter autoclave, 100 parts of water, 0.6 parts of sodium dodecylbenzenesulfonate, 0.3 parts of sodium bicarbonate, 0.8 parts of potassium persulfate and the first-stage monomer mixture shown in Table 4 , A chain transfer agent, and a cyclic unsaturated hydrocarbon having one unsaturated bond in the ring were charged, and the first polymerization was carried out at 60. When the conversion of the first stage reaches 7.5%, the monomer mixture of the second stage, chain transfer agent, and unsaturated hydrocarbon are continuously added in 6 hours, and the second stage polymerization is performed at 70 ° C. Was performed. Thereafter, in order to complete the polymerization, the reaction was continued for another 3 hours to terminate the polymerization. The polymerization conversions were all 98% or more. After adjusting the pH of the obtained copolymer latex to 8 using sodium hydroxide, unreacted monomers and unsaturated hydrocarbons remaining as unreacted substances are removed by steam distillation. Polymer latexes 14 to 20 were obtained.

 Preparation of adhesive composition for carpet backing

Each of the copolymer latexes 14 to 20 was adjusted to pH 8.5 with an aqueous sodium hydroxide solution. For 100 parts (solid content) of each pH-adjusted latex, Aron T 40 (manufactured by Toagosei Co., Ltd .: low molecular weight sodium polyacrylate) was used as a dispersant, 1.0 part and heavy calcium carbonate 4 each. 0 parts were added, and Alon as a thickener was added. 20 parts (manufactured by Toagosei Co., Ltd .: high-molecular-weight sodium polyacrylate) was added, and the solid content was reduced to 7 by ion-exchanged water. Adjusted to 5% by weight, Adhesive composition for carpet backing with a viscosity of 1700 to 2000 centimeters (BM type viscometer, 12 rpm, # 4 rotor, 20 ° C) I got something. The resulting adhesive composition base fabric of polypropylene split tree Toyan, pies Le is the back surface of Tafutetsu Dokape' bets fabric is a nylon 6 of 1 Z 8 inch gauge in apparent weight 1 ² 0 O g / m 2 And apply a 7 oz squared yard backing of jute woven fabric on it, for 20 minutes at 120 ° C It was dried to give a carpet lined with jute.

 Using these force units, the adhesive force is measured in accordance with JIS 1021, and the force is measured.

 Next, the thus prepared carpet was immersed in ion-exchanged water at 20 ° C. for one hour, and then the adhesive strength was measured according to JIS 1021.

 In addition, a test piece of 1 O cm x 1 O cm was prepared, the test piece was placed in a glass bottle capable of being sealed, left at 50 ° C for 1 hour, and the degree of odor was determined by removing the stopper.

 〇: Almost no smell

 △: Slightly smell-X: Smell

Table 5 shows the results.

Table 1 4 Example Comparative example Latex No. 1 A 10

 丄 4 1 丄 b 1171 Ιο 19 20 Butagen 16/24 15/35 9/51 12/48 14/56 13/35 9/51

-7 1

90 no 10 no 0 c / no

 0 / ώθ 0 / LL 0 / LL 13 / 29.5 5/22 Methyl metal clear 2/3 2/3

Acrylonitrile 1/4 2/8 8 β-Hydroxyshetyl acrylate-/ 1 0.5 /--/ 1 0.5 /-

Fuma Zole / _ Unoichi

 / / 丄 / 2 /-1 / -1 Acrylic acid 1/1 1-1 / 1 1 / 1-1 / 1 Itaconic acid 2 /-Cyclopentene 5 / —

 6/4 4 /-6 /-11-

Ci — methyl styrene dimer 0.3 / —

η-Dodecyl mercapone 0.3 /-0.1 / —0.1 / —0.11-0.3 / —0.2 / —t-Dodecyl mercapone 1 / 0.4-/ 0.4 0.1 / 0.6 -/ 0.7 1 / 0.5-/ 0.3-/ 1.0 Reactor contamination 〇 〇 〇 〇 〇 Δ X Fine solids 〇 〇 〇 〇 XX XX Gel included 50 52 58 62 67 72 63

Table 1 5

Polymerization example 3 of copolymer latex

 In a 20-liter autoclave, 100 parts of water, 0.8 parts of sodium dodecyl benzene sulfonate, 0.3 parts of sodium bicarbonate, 0.9 parts of potassium persulfate and the first-stage monomer shown in Table 6 The mixture, the chain transfer agent, and a cyclic unsaturated hydrocarbon having one unsaturated bond in the ring were charged, and the first-stage polymerization was performed at 65 ° C. When the first-stage conversion reaches 80%, the second-stage monomer mixture, chain transfer agent, and unsaturated hydrocarbon are continuously added in 8 hours, and the second-stage polymerization is performed. Was.

Thereafter, to complete the polymerization, the reaction was continued for another 3 hours to complete the polymerization. All polymerization conversions were 98% or more. After adjusting the pH of the obtained copolymer latex to 8 with sodium hydroxide, unreacted monomers and unsaturated hydrocarbons remaining as unreacted substances were removed by steam distillation. ~ 26. Preparation of adhesive composition for fiber base material

 For each 100 parts (solid content) of the copolymer latex 21 to 26, 2 parts of zinc white, 1 part of dibutyldithiocarbamine-zinc and 1 part of antigen S (styrene phenol: Sumitomo Chemical Co., Ltd.) ) Is added, 0.3 parts of carboxymethylcellulose is added as a thickener, and the solid content is adjusted to 48.0% by weight with ion-exchanged water. (BM type rotational viscometer, 60 rpm # 3 rotor, 20 ° C.) to prepare an adhesive composition for a lock fiber base material.

 These adhesive compositions were adjusted to a solid content of 40.0% by weight with ion-exchanged water, and the length was 100 mm, the width was 100 ffim, the thickness was 20 dragons, and the weight was 3.0 g. Approximately 2 g of the surface of one-mook fiber was spray-coated and dried at 80 ° C for 10 minutes. Further, the back surface was similarly spray-coated, and dried at 80 ° C. for 10 minutes. Thereafter, the mixture was heated at 130 ° C. for 15 minutes to promote cross-linking to prepare a lock test piece. Using these test pieces, tests of adhesive strength and water-resistant adhesive strength were performed. Table 6 shows the results.

 Adhesive strength: Measured with an Instron tensile tester.

Adhesive strength after immersion: Each lock test piece was immersed in ion-exchanged water at 20 ° C, and then measured with an Instron tensile tester.

I Table 1 6

 Example Comparative example Futex N 0.? 1? 9fi god 2/18 4/21 0/40 8/42 5/40 8/47 styrene 7 / 59.5 10/57 3/30 7 / 39.5 4/39 6 / 35.5 No.Meter Crate 1/9 0.5 / 4.5 2/18 1/9

 Κα, τ_ key; rare |] shik 1 /--/ 1 1 /-1 /-itaconic acid 1 /-1 /-1 /-fumaric acid 2 /-ac Linoleic acid 1.5 /-11- 1.5 /-1.5 /-Cyclopentene 3 /-

Cyclohexene 5/5 5 /-4 /-Cyclic mouth Hexane 5 /-t-dodecylmethylcaptan-/ 0.5 0.1 / 0.3 0.1 / 0.8 0.2 / 1.0 0.1 / 0.9 0.2 / 1.2 Reactor fouling 〇 〇 〇 X Δ X Fine solids 〇 Δ 〇 〇 XX Gel content 62 55 45 40 59 55 Bonding strength ( _kg / _cm ² ) 3.5 3.1 3.3 3.9 2.7 2.6 Adhesive strength after immersion (kg / cm ² ) 2.6 2.8 2.7 2.4 2.1 1.6

Hereinafter, the invention of the seventh item will be specifically described.

 Water retention

Apply the paper coating composition to a high-quality paper using a single wire with a wire bar. <0 seconds immediately after coating, measure the time until the surface of the coating layer loses moisture and loses gloss. The value is regarded as water retention. Water retention The larger the value is good _c gravure printability

 Using a gravure printing press of the Ministry of Finance, printing was performed using a dot gravure plate, the halftone misdots were counted, and classified into A (excellent) to D (poor) and judged.

Preparation of copolymer latex,

In a 20 liter autoclave, 100 parts by weight of water, 0.4 part of sodium dodecylbenzenesulfonate, 0.3 part of sodium hydrogen carbonate, 1.0 part of potassium persulfate and 1 shown in Tables 7 and 8 monomeric compound of stage, RensaUtsuri transfer agent, and polymerization was carried out in the first stage a cyclic unsaturated hydrocarbon having one unsaturated bond in the ring with the charged 7 0 ^e C. When the conversion of the first-stage emulsion polymerization reaches 70%, the monomer mixture, the continuous transfer agent, and the unsaturated hydrocarbon in the second stage are continuously added in 6 hours, and the second-stage polymerization is performed. Was performed. Thereafter, in order to complete the polymerization, the polymerization was further continued and terminated at a polymerization conversion rate of 97%. After adjusting the pH of the obtained copolymer latex to 8 using sodium hydroxide, unreacted monomers and unsaturated hydrocarbons remaining as unreacted substances are removed by steam distillation. Polymer latexes 27 to 37 were obtained.

 In the table, the left side shows the amount of the first stage and the right side shows the amount of the second stage across "Z".

Preparation example 1 of paper coating composition 1

Using copolymer latex 27-29 and 34-35, adjust with pure water to a solid concentration of 60% based on the following formulation, and coat with paper Compositions 1 to 5 were prepared. Table 9 shows the fluidity and water retention of the obtained paper coating composition.

 (Prescription)

 No. 1 kaolin 80 0

 Heavy calcium carbonate 20 parts

 0.5 parts of dispersant

 0.2 parts of sodium hydroxide

 8 parts of copolymer latex

 Thickener 0.5 part Solid content 60%

Preparation Example 1 of paper coating composition 2

 Using the copolymer latex 30-33 and 36-37, each was adjusted with pure water to a solid content of 63% based on the following formulation, and the composition for paper coating was 6-10. Was prepared. Table 10 shows the fluidity and water retention of the obtained paper coating composition.

 (Prescription)

 No. 1 kaolin 80 0

 Heavy calcium carbonate 20 parts

 0.5 parts of dispersant

 0.2 parts of sodium hydroxide

 Colate latex 6.5 parts

Oxidized starch 2 parts Solid content 6 3% Creating coated paper for gravure printing

Commercial fine paper (6 4 £ Bruno 111 ²⁾ in the paper coating composition a coated amount of the single-sided 1 3 gZ m to ² and so as was applied by using a wire lock Tovar immediately 1 4 0 ° C It was dried with a hot air dryer. After humidity control, a super calender treatment was performed to obtain a coated paper.

Table 9 and Table 10 show the gravure printability of the obtained coated paper.

Fine

Table η t a 11 7

 Remedo Example

No. 27 28 29 30 31 32 33

 Russi

Butter with jean

 Suno 5/40 7/41 8/42 15/45 6/54

3/57

 H 11/59

 Thimeme 4/37 5/32 5/25 8/28 3/24 1/26

3/19 relay

Ma 1/9

 Renono 1/9 1/9 1/4 1/4 1/9

 / 1/4

 Relento Re Nore — / 5

METACRI Ρ -2

β'-Hydroxyshechirakry-Pupit-1 / 1-1 11 // 1 1 /

A

 Cryllami 2 /-1 / —

夕 コ タ タ タ タ タ タ タ タ

Full II-acid II-1 / -methacrylic acid 1 —I

Acrylic acid 1 / · 1 /-

3 / — 4/2 I-sh 4 /

 C to D

 Putten 2 / —

Thick mouth

 0.5 / —

 / 0. 5-/ 0. 3 0. 1/0. 3-/ 0. 3 0. 2/0. 8-/ 0. 5-/ 0. 9

0.2 /-0. 1 /-0. V- Solid 〇 〇 〇 〇 〇 〇 〇 (%) 87 88 91 90 85 87 82

3 I

Table 1 8

 Comparative example

 Copolymer latex No. O A

 04 00 00 0 1 Butagen 3/22 8/42 9/51 9/51

 Z C ノ β

 Styrene 0/00 β D / 3oΠU

 Methyl metal crelay 11/1 Q y1 1 A 丄 1/44 44 丄 / ^ Acrylonitrile

 / Ό

 ノ ソ ソ ソ ソ ソ ； ；

 ー レ π

 P ,,,,,,,,,,,,,,,,,,, 11

 Γ 1 / -1 1 /-1 /-1 /-

 Itaconic acid 11- 2 / — 1 / — .2 /-Fumanoleic acid 1 1

 1 / 丄 / one—

 J Jit Λ

 K'no 1so1) \ oh

 Nore

 Acrylic acid 1 / — 1 / 1-cyclopentene

 Cyclo to 4 /-Cyclo to tent

 Cyclohexan 11-a ー Methynorestilylene dimer 0.3 / —

 t -one do not transfer Meso captan-/0.3.1/0.0.6 0. 2 / 1.2-/0.5 .5 n--do not transfer meso captan

Fine solids O ΔX Δ Gel content (%) 85 88 86 87

Table 9

Table 1 0 Example of practice Comparative example Latex No. 3 0 3 1 3 2 3 3 3 6 3 7 Flowability (cps) 4 8 4 7 4 6 4 7 5 4 5 4 Water retention (seconds) 1 4 1 3 1 3 1 4 1 0 1 1 Gravure printing suitability BBBBBB Hereinafter, the invention of the eighth paragraph will be specifically described.

 Chromogenicity

In an atmosphere of 5 ° C, Align superimposed lower paper created a commercially available upper paper and the present invention, low better coloring property of _c numerical measuring the whiteness aging is entirely developed with super calendering pressure was good It can be said that.

Polymerization of copolymer latex.

 In a 20 liter autoclave, 100 parts by weight of water, 0.4 part of sodium dodecylbenzenesulfonate, 0.3 part of sodium bicarbonate, 1.0 part of persulfuric acid rim and Table 11 or Table 11 The first-stage monomer mixture, chain transfer agent, and unsaturated hydrocarbon shown in 112 were charged and the first-stage polymerization was performed at 70 ° C. When the conversion of the first-stage emulsion polymerization reaches 70%, the second-stage monomer mixture, chain transfer agent, and unsaturated hydrocarbon are continuously added in 6 hours, and the second-stage polymerization is performed. Natsuta. Thereafter, in order to complete the polymerization, the polymerization was further continued and terminated at a polymerization conversion rate of 97%. After adjusting the pH of the obtained copolymer latex to 5 using sodium hydroxide, unreacted monomers and unsaturated hydrocarbons remaining as unreacted substances are removed by steam distillation to obtain a copolymer. Latex 38-47 was obtained.

In the table, the left side shows the amount of the first stage and the right side shows the amount of the second stage across "Z".

Table 1 1 1

 Example

Copolymer latex No. 38 39 40 41 42 Butagen 3/27. 6/36 6/44 3/22 3/27 Styrene 5/45 5/32 5/24 6/47 6 / 47 Evening 0

 No evening! ) A / a 1 / A 0/1

 1 // 1

 0 丄 / 1 NO Q-acrylonitrile-/ 7 2/10 2/13 0.5 / 4 Itaconic acid V- 11- 2 /-Fumaric acid 11- 15 /- Acrylic acid 1 / -1 1 / -1 1/1 Metal linoleic acid 1 / -1

 To the mouth to the mouth 2 /-5 /-3/2 3 /-3 /-To the mouth to the mouth

t 1/0. 1 0. 1/0. 2 0. 1/0. 1 0. 1/0. 1 0. 1 / 0.5.5 Includes Amount (%) 88 85 91 82 63

Table 1 1 2

 Example Comparative example Copolymer latex No. 43 44 45 46 47 Butadiene 4/31 3/30 3/27 9/61 2/13 Styrene 丄 4/44 No

 2/15 9/63 Methyl methacrylate 2/13 1/4 1/9 1/4 Acrylonitrile 1/4 2/10 -11 1/9 1/4 Taconic acid 2 /-3 /-3 /-Fumaric acid 1 /-Acrylic acid 2/8 1/1 1/1

Methacrylic acid

To the mouth 3 /-3 /-5 /-2 /-To the mouth 2 /-t-Dodecinolene captan 0.1. 1/0. 7 0. 1 / — 0. 1/0. 5 0. 1/0, 1 Gel Content (%) 81 52 93 84 77

Preparation of developer composition

 According to the composition shown below, a developer composition was prepared. The developer used was a phenol resin that had been treated in advance with a ball mill for 24 hours.

 Heavy calcium carbonate 0 0 Dry parts by weight Developer (phenol resin) 20

 P VA 5

 Oxidized starch 1 0

 Latex 1 0

 50% solids

Creating the bottom sheet

The developer composition was coated on a commercially available high-quality paper (64 g / m ² ) with a diabar so that the developer composition became 7 g / cm ^2, and immediately dried in a 100 ° C. oven. The coated paper was humidified overnight to prepare the lower paper. The resulting paper was evaluated for color development, RI Dry Pick and RI Wet Pick. The results are shown in Table 13.

Table 1 13 Examples Comparative examples

38 39 40 41 42 43 44 45 47

30 seconds 28.4 30.6 31.7 30.7 30.2 27.9 32.3 34.4 44.5 29.6 Color development

 (Blue) 60 seconds 26.4 27.3 28.6 27.5 27.0 25.8 29.7 31.9 41.0 26.6

I 1 says 18.1 18.7 18.6 18.8 18.3 17.5 19.4 21.2 23.8 18.3O

R I Dry Pick 4.5 5.0 5.0 4.0 4.2 4.5 3.8 2.5 3.0 1.0

RI Dry Pick 4.5 4.3 4.0 4.2 5.0 4.0 4.0 2.0 1.5 1.0

Hereinafter, the invention of the ninth aspect will be specifically described.

 Preparation of copolymer latex

 In a 10 liter autoclave, 100 parts by weight of water, 0.4 part of sodium dodecylbenzenesulfonate, 0.3 part of sodium bicarbonate, 1.0 part of potassium persulfate and Table 14 or Table 15 The first-stage polymerization was carried out at 65 ° C. by charging a first-stage monomer mixture, a chain transfer agent, and a cyclic unsaturated hydrocarbon having one unsaturated bond in the ring as shown in (1). When the conversion of the first-stage emulsion polymerization reached 65%, the second-stage monomer mixture, chain transfer agent, and unsaturated hydrocarbon were continuously added in 7 hours, and the second-stage polymerization was started. Done. After completion of the second-stage monomer addition, the dissimilarity transfer agent and the unsaturated hydrocarbon were continuously added over 2 hours, and the polymerization was continued until the polymerization conversion reached 97%, and the polymerization was terminated. After adjusting the pH of the obtained copolymer latex to 8 using sodium hydroxide, unreacted monomers and unsaturated hydrocarbons remaining as unreacted substances are removed by steam distillation. Polymer latexes 48 to 56 were obtained.

 In the table, the left side is the first stage, the center is the second stage, and the right side is the amount after the completion of the second stage, after "ZZ".

Preparation of paint for paper coating (I)

 Each of the copolymer latexes 48 to 50 and 55 was adjusted with pure water so as to have a solid content of 62% based on the following treatment, respectively, to obtain a paper coating coating.

(Prescription I)

 Kaolin clay 80 parts

 Heavy calcium carbonate 20 parts

Modified starch 5 parts Copolymer latex 2 parts (solid content) Solid content .62%

After coating and drying a commercially available high-quality paper (64 gZm ² ) using a coating bar so that the coating amount of the above composition is 13 g / m ^{2 on} one side, the roll temperature is 50 ° C., and the linear pressure is 70 ° C. Super calendering was performed under the condition of ~ 8 OkgZcm to obtain a coated paper.

 The obtained coated paper was measured for RI Wet Pick, RI Dry Pick, and blister resistance. .

Preparation of paint for paper coating (Π),

 Using Copolymer Latex 5:! To 54 and 56, each was adjusted with pure water so as to have a solid concentration of 62% based on the following treatment, to obtain a paper coating coating.

(Prescription Π)

 Power Olin Clay 60 parts

 Heavy calcium carbonate ■ 40 parts

 Modified starch 6 parts

 Copolymer latex 10 parts (solid content) Solid content 62%

After coating and drying the commercially available high-quality paper (64 gZm ² ) using a coating bar so that the coating amount of the above composition is 1 OgZm ^{2 on} one side, the roll temperature is 50 ° C., and the linear pressure is 70 to 90 ° C. Super calendering was performed under the condition of 8 Okg / cm to obtain a coated paper.

The obtained coated paper is RI Wet Pick, RI Dry Pick, The _c results of measuring the blister properties shown in Table 1 6.

Table 14

 Examples

 α 1 Noonono AIM 0, O 40 en 01 CO Butagene 3/27 / — 5/30 / one 5/30 / — 4/36 / — 4/36 / — 4/44 / one> "7 no 1 A / Q0 / —— β / 00 / one fi / 00 / —At07 / — / 0 / „

 f 01 / mesta no u u no hit Hit no nin 9/1/1 / O 9f / 1 u /// ― // IV ― 1 f / 5f / ― 11 Q / ― 二 2 り 9 / R / ― 1 / Qf /-1 / q / — / o /

 3—In the light. Quinche, acrylate 1/1 / -1 — 1 1 / -1 — 1 1 /-2/1/1 / Acrylic amide 1/1/1 — / 1 /-Fumanoleic acid 1 / — 1 One 2 / 'one / one 2 / one / one

 Itaconic acid 2/1/1 2/1 / — 2/1/1

4 ^

 Acrylic acid 2 /-/-1/1/1/1/1/1 / \ Methacrylic acid — 1 1/1/1/1/1 1 1-cyclopentene 4 / One / one

 Cyclone 3/2/3/2/2 6 / --1 2 6/1/2 4 / 1/1

 Thick mouth

t- にTan 0.05 / 0.5 / 0.05 0.1 / 0.7 / 0.1 0.1 / 0.7 / 0.1-/ 0.9 / 0.1 1 / 0.9 / 0.1-/ 0.5 / 0.1 a-methylstyrene

Table 1 1 5

 Example Comparison example

Copolymer Lux No. 54 55 56 Butadiene 5/47 /-5/30 / -1 4/36 / --Styrene 6/29 /-6/32 / -1 4/37 / -1 Evening knoll 1) Zor 西 west MX // Z レ * '1/9 / ― 2/13 / 1-1 / 5/1 ロ ロ 二 1/4 / -1 2/6 /-1 / 9 / one meta-tril

 ー t Dokijechiru end clear 1/1 / ― ― f / 1 / acrylamide 1/1 / ―

Fumanoleic acid 2 / — / mono-itaconic acid 3 / one / one r 2 »/ one / one

Acrylic acid 1/1 /-/ Methacrylic acid 1/1 / -1

 Pen mouth Penten

 Xenon to the mouth

 Thick mouth Hepten 3/1/2

6/2/1 t— 2'Silmer cuff. 0.05 / 1.0 / 0.3 0.1 / 0.7 / 0.1-/ 0.9 / 0.1a

Table 1 16

 Example Comparative Example Example Comparative Example Copolymer latex Nc 48 49 50 55 51 52 53 54 56 Paint formulation I I I I Π Π Π Π Π

R I Dry Pick 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.5

RI Wet Pick 1.0 1.0 1.0 4.0 1.0 1.0 1.0 1.5 2.0 Benostar resistance (° C) 240 230 235 200 235 230 225 220 205

Copolymer latex No. 49 except that the continuous transfer agent to be added after the completion of the second-stage monomer addition was added in the second stage, and the chain transfer agent was not used after the completion of the second-stage monomer addition The copolymer latex obtained by performing the same operation as in the preparation of No. 4 was inferior in blister resistance and RI Wet Pick as compared with the yarn using the No. 49 latex.

 Further, the invention of Item 10 will be specifically described below.

 Resistant / 'sticking mouth stain'

 A coated paper sample (Super Power Render, unprocessed product) is superposed on the polyester film so that the coated surface is in contact with it, and then heated with a 20 O kg hot roll heated to 120 to 130 ° C. Heat press. The dirt adhering to the polyester film is visually judged, and the backing roll dirt resistance is evaluated.

 1.0 (good with little dirt) to 5.0 (many dirt and bad)

Preparation of copolymer latex ''

In a 10 liter autoclave, 100 parts by weight of water, 0.4 part of sodium dodecylbenzenesulfonate, 0.3 part of sodium bicarbonate, 1.0 part of potassium persulfate and the first stage shown in Table 17 The first-stage polymerization was carried out at 65 by charging a monomer mixture, a chain transfer agent, and a cyclic unsaturated hydrocarbon having one unsaturated bond in the ring. When the conversion of the first-stage emulsion polymerization reached 70%, the second-stage polymerization was carried out by continuously adding the monomer mixture and the chain transfer agent in the second-stage for 0.6 hours. Thereafter, the third-stage monomer mixture and the chain transfer agent were continuously added in one hour to carry out the third-stage polymerization. In order to complete the polymerization, the reaction was further continued, and the polymerization was completed at a polymerization conversion rate of 9. After adjusting the pH of the obtained copolymer latex to 8 using sodium hydroxide, unreacted monomers and unsaturated hydrocarbons remaining as unreacted substances are removed by steam distillation to obtain a copolymer. Latexes 57 and 58 were obtained. The copolymer latex 59 was polymerized in the same manner as the copolymer latex 58 except that cyclohexene was changed to cyclohexane. Hereinafter, copolymer latex 59 was obtained in the same manner as copolymer latex 58. In the table, the left side is the first stage, the center is the second stage, and the right side is the amount after the completion of the second stage, after "ZZ". .-Preparation of paint for paper coating (I)

 The copolymer latex 57 was adjusted to have a solid content of 62% based on the following formulation using pure water to obtain a paper coating paint.

 (Prescription I)

 Kaolin clay .80 parts

 20 parts of heavy calcium carbonate

 Modified starch 5 parts

 Copolymer latex 12 parts (solid content) Solid content 62%

The composition was coated on a commercially available high-quality paper (64 gZin ² ) using a coating bar such that the coating amount of the composition was 13 g / m ^{2 on} one side, and dried to obtain a coated paper. The obtained coated paper was evaluated for resistance to backing roll stain.

 The obtained coated paper was subjected to a super calender treatment under the conditions of a roll temperature of 50 ° C and a linear pressure of 70 to 8 OkgZcin, and then RI Dry Pick was measured. Preparation of paint for paper coating (Π)

 Using the copolymer latexes 58 and 59, T was adjusted using pure water based on the following formulation so that the solid content concentration became 62%, to obtain a paper coating paint. (Prescription Π)

Kaolin clay 60 parts 40 parts of heavy calcium carbonate

 Modified starch 6 parts

 Copolymer latex 10 parts (solid content) Solid content 62%

The composition was coated on a commercially available high-quality paper (64 gZm ² ) using a coating bar such that the coating amount of the composition was 1 OgZm ^{2 on} one side, and dried to obtain a coated paper. The obtained coated paper was evaluated for resistance to backing roll stain.

 -The obtained coated paper was subjected to super calender treatment under the conditions of a roll temperature of 50 ° C and a linear pressure of 70 to 8 Okg / cm, and then RI Dry Pick was measured. Table 18 shows the results.

A copolymer latex having the same monomer composition as copolymer latex No.57 except that the monomer to be added after the completion of the second-stage monomer addition was added to the first or second stage. The RI Dry Pick and the backing roll stain resistance were inferior to the yarn using the No. 57 latex.

Table 1 17

 Example i i 1 乂 * Example V'S copolymer latex No. 57 58 59

 ノ ■ »ノ

Nog u u 1 1 ϋ 1 1 5/35 /-Chill 7/33/5 3/25/7 3/25/7 M Evening linole B Metinor 1/4/10 1/6 / 3 1/6/3 acrylonitrile 1/4 /-1/8/1 1/8/1 metal acrylonitrile

 -Hydrokin etilakri o /

 1/1/1 11-1-11-1-

Fumaric acid 9 / — / —

Itaconic acid 2 /-/ 1 1 1-1-Acrylic acid 1/1/1

Methacrylic acid 1/1 / 1-1

 Cyclopenten 4 / one / one

 Cyclohexene 6 /-/ one

Cyclohexane 6 /-/ 1 t-1-dodecyl melamine carb-10.5 / 0.1-10.5 / 0.2 1 / 0.5 / 0.2 a--Methyl styrene dimer 0.2 /-1 one

Table 18

 Example Comparative Example Copolymer latex Nc 57 58 59 Gel content (%) 48 78 83 Paint formulation I Π Π

R I Dry Pick 2.5 1.3 2.3

Ul

o

Ha ' ₇ kink resistance "Peel resistance 1.3 2.3 2.6

Claims

The scope of the claims  1. Emulsion polymerization of aliphatic conjugated monomer and other copolymerizable monomer in the presence of a cyclic unsaturated hydrocarbon having one unsaturated bond in the ring. A method for producing a copolymer latex.  2. 1 to 80% by weight of aliphatic conjugated diene monomer, ethylenically unsaturated rubonic acid monomer 0.5 to 10% by weight, and another monomer copolymerizable with these 1 The method for producing a copolymer latex according to claim 1, wherein a monomer mixture consisting of 0 to 89.5% by weight is used.  . 3. The method for producing a copolymer latex according to claim 1, wherein 0.05 to 10 parts by weight of a chain transfer agent is used per 100 parts by weight of the monomer mixture.  4. An adhesive composition containing the copolymer latex obtained by the production method according to claim 1 or 2.  5. A paper coating composition comprising the copolymer latex obtained by the production method according to claim 1 or 2.  6. An adhesive composition for a car backing, comprising the copolymer latex obtained by the production method according to claim 1 or 2.  7. An adhesive composition for a lock fiber base material, comprising the copolymer latex obtained by the production method according to claim 1 or 2. 8. In a gravure printing paper coating composition containing a pigment and a copolymer latex as a binder, the copolymer latex may contain 30 to 80% by weight of an aliphatic conjugated monomer, 0.5 to 10% by weight of unsaturated carboxylic acid monomer and another monomer capable of copolymerizing with these. 10 to 69.5% by weight, and unsaturated bond in the ring. A gravure printing paper coating composition characterized in that it is a copolymer latex obtained by emulsion polymerization in the presence of a cyclic unsaturated hydrocarbon having a carboxylic acid. 9. The gravure printing paper coating composition according to claim 8, wherein the chain transfer agent is used in an amount of 0.05 to 0.5 part by weight per 100 parts by weight of the monomer mixture.  10. A developer composition for a pressure-sensitive copying paper containing a pigment, a developer and a copolymer latex as a binder, wherein the copolymer latex is an aliphatic conjugated diene monomer 20 to 60% by weight, vinyl cyanide monomer 0 to 20% by weight, ethylenically unsaturated carboxylic acid monomer 1 to 20% by weight and other monomers copolymerizable with these 0 Pressure-sensitive copying paper characterized in that it is a copolymer latex obtained by polymerizing milk in the presence of up to 79% by weight of a cyclic unsaturated hydrocarbon having one unsaturated bond in the ring. Developer composition.  11. The developer composition for pressure-sensitive copying paper according to claim 10, wherein 0.05 to 10 parts by weight of a continuous transfer agent is used per 10 G parts by weight of the monomer mixture.  1 2. Copolymerizable with aliphatic conjugated diene monomer, ethylenically unsaturated carboxylic acid monomer and these in the presence of a cyclic unsaturated hydrocarbon having one unsaturated bond in the ring A process for producing a copolymer latex, which comprises adding a part of a chain transfer agent after completion of addition of a monomer when emulsion-polymerizing other monomers.  1 3. In the presence of a cyclic unsaturated hydrocarbon having one unsaturated bond in the ring, an aliphatic conjugated diene monomer (ii). In the emulsion polymerization of another monomer (8) copolymerizable with the above, after the addition of the monomer mixture containing the above component (i), the monomer mixture containing no component (ii) is further added. A method for producing a copolymer lattetus, characterized in that: 1 4. Aliphatic conjugated diene monomer 10 to 80% by weight, ethylenically unsaturated carboxylic acid monomer 0.5 to 10% by weight and other monomers copolymerizable with these 1 14. The method for producing a copolymer latex according to claim 12, wherein a monomer mixture comprising 0 to 89.5% by weight is used. 15. The process for producing a copolymer latex according to claim 12, 13 or 14, wherein 0.05 to 10 parts by weight of a chain transfer agent is used per 100 parts by weight of the monomer mixture. .  1 6. An adhesive composition comprising the copolymer latex obtained by the production method according to claim 12 or 13.  1 7. A paper coating composition comprising the copolymer latex obtained by the production method according to claim 12 or 13.  18. An adhesive composition for a backing of a force-bet, comprising the copolymer latex obtained by the production method according to claim 12 or 13.  1 9. An adhesive composition for a lock fiber base, comprising the copolymer latex obtained by the production method according to claim 12 or 13.